1 - acylbicyclo(1.1.0)butanes,their homopolymers and their 1-acyl-3 - halocyclobutane precursors,and their preparation



United States Patent ABSTRACT OF THE DISCLOSURE 1-Acylbicycl0[1.1.0]butanes of the formula where R is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R -R are hydrogen or selected hydrocarbyl groups.

1-Acyl-3-halocyclobutanes of the formula R3 C-R where R R are defined as above and X is a halogen.

Homopolymers of (1) which are solid, thermoplastic polymers of high molecular weight.

The process of dehydrohalogenating compounds of Formula 2 with a dehydrohalogenating agent to obtain compounds of Formula 1.

The process of polymerizing a compound of Formula 1 to obtain a homopolymer.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to l-acylbicyclo[l.l.0]butanes and their homopolymers; to 1-acyl-3-halocyclobutane precursors; and to their preparation.

Description of the art Of the art which has come to the attention of the applicant prior to the filing of this application, no references describing l-acylbicyclo[1.1.0]butanes or their 1-acyl-3- halocyclobutane precursors were found.

SUMMARY OF THE INVENTION The novel compositions of this invention are those selected from the group consisting of:

(A) A 1-acylbicyclo[l.l.0]butane represented by the formula i R3 C-R wherein R is hydrogen, hydrocarbyl of 1 to 19 carbon atoms, or substituted hydrocarbyl of 1 to 19 carbon atoms in which the substituents are selected from halogen (fluoro, chloro or bromo), lower alkoxy or mixtures thereof; and R through R individually, are each hydrogen or hydrocarbyl of 1 to 19 carbon atoms that is free of aliphatic unsaturation (i.e., free of aliphatic ethylenic or acetylenic carbon-to-carbon bonds);

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(B) A 1-acyl-3-halocyclobutane represented by the formula wherein R through R are each defined as above and X is halogen of atomic number 17 through 53 (chlorine, bromine or iodine); and

(C) A homopolymer of 1-acylbicyclo[1.1.0]butane represented by the recurring unit fi R2 R10 11 wherein R through R are each defined as above, It is a DESCRIPTION OF THE PREFERRED EMBODIMENTS The term hydrocarbyl as used herein in the definition of R represents radicals composed of hydrogen and carbon. It may be alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, aralkenyl, and the like. The term hydrocarbyl free of aliphatic unsaturation as used herein in the definitions of R through R represents radicals such as alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and the like.

Preferably, R, in any of the above formulas is hydrogen, lower alkyl or phenyl; while R through R are each hydrogen or lower alkyl. More preferably, R R R and R are each hydrogen; while R is hydrogen or lower alkyl, X in Formula 2 is preferably chlorine.

The 1-acyl-3-halocyclobutanes of Formula 2 may be prepared by the reaction of a Grignard reagent RMgX with a l-cyano-3-halocycl0butane followed by acid hydrolysis, as described in Examples 1 and 2. They may also be prepared by treating a l-cyano-3-alkylenecyclobutane with a Grignard reagent RMgX to obtain a l-acyl- 3-alkylenecyclobutane to which HX is then added to obtain a 1-acyl-3-halo-3-alkylcyclobutane, as described in Examples 4 and 5. In the reaction of a 1-cyano-3-halocyclobutane with a Grignard reagent RMgX Where R is alkyl or cycloalkyl, there is formed in addition to a 1-acyl-3-halocyclobutane, as a by-product the corresponding 1-cyanobicyclo[1.1;0]butane. If sufiicient Grignard reagent is present, it reacts with the l-cyanobicyclo[1.1.0] butane to yield the corresponding 1-acylbiocyclo-[l.1.0] butane.

The dehydrohalogenation process of this invention is carried out by the action of a dehydrohalogenating agent. Suitable agents include alkali metal hydn'des such as sodium hydride, lithium hydride, and the like, and other strong bases such as potassium t-butoxide, sodium methoxide, and the like. The dehydrohalogenation may be carried out at temperatures in the range of to C. It is convenient, though not essential, to carry out the dehydrohalogenation in the presence of a reaction medium which is inert to the reactants and products. Suitable media include ethers such as diethyl ether, the dimethyl ether of ethylene glycol, tetrahydrofuran, and the like,

dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like. The reaction may be carried out in air, but best yields are obtained when an inert atmosphere is employed, such as nitrogen, helium argon, and the like.

Compounds of Formula 1 wherein R is hydrogen are prepared by reacting a hydrocarbyl 3-chlorocyclobutane carboxylate with lithium tri-tert-butoxyaluminohydride in tetrahydrofuran, as described in Example 3, to obtain 3- chlorocyclobutane carboxaldehyde, which is dehydrohalogenated as described above.

The homepolymers of this invention are prepared by reacting a l-acylbicyclo[1.1.0]butane monomer in bulk, dispersion, emulsion or in solution in an inert organic solvent at a temperature of -100 to 160 C. in the presence of an initiator selected from a free-radical-generating initiator, an anionic initiator, a cationic initiator, or a coordination-type initiator.

The free-radical-generating initiators may be selected from a wide variety of compounds representative of this type of initiator. Included are the azo initiators, for example, a,a-azodiisobutyronitrile, 1,1'-azodicyclohexanecar bonitrile, dimethyl a,a-azodiisobutyrate and a,a-azodiisobutyramide, and the organic peroxides and hydroperoxides, for example, dibenzoyl peroxide, di-t-butyl peroxide, and t-butyl hydroperoxide. The initiators can be used in proportions ranging from 0.01 to weight percent of the monomer being polymerized. Other sources of free radicals for initiating polymerization may also be used such as electron bombardment, ultraviolet light in the presence of a sensitizer, and the like. Free-radicalgenerating initiators are preferred with monomers of Formula 1 in which R is hydrogen.

Suitable solvents and/ or dispersion media for the freeradical polymerization include water, hydrocarbons such as benzene and hexane, chlorinated aromatic hydrocar bons such as chlorobenzene, nitriles such as acetonitrile, amides such as dimethylformamide and N-methylpyrrolidone, sulfoxides such as tetramethylenesulfoxide and the like. As indicated above, it is not essential that a solvent or dispersion medium be used, and bulk polymerizations can be carried out.

A wide variety of anionic initiators are operable herein for the polymerization of 1-acylbicyclo[l.l.0]butanes. Representative anionic initiators that can be used include the alkali metal alkyls, for example, n-butyllithium and methyllithium; the alkali metal alkoxides, for example, potassium t-butoxide and sodium methoxide; and the alkali metal aryls, for example, sodium naphthalene. The concentration of anionic initiator employed can range from 0.01 to 10 weight percent of the monomer being polymerized. The order of addition of the monomer and the initiator is not critical.

Suitable reaction media for the anionic polymerization include ethers, for example, diethyl ether, tetrahydrofuran, and the dimethyl ether of ethylene glycol; hydrocarbons, for example, benzene and hexane; chlorinated hydrocarbons, for example, chlorobenzene; and amides, for example, dimethylformamide. The ethers are preferred.

Representative cationic initiators which may be used include boron trifluoride and trichloride, aluminum trichloride, silicon tetrafluoride, phosphorus and arsenic triand pentafluorides and chlorides, aluminum tribromide, titanium tetrachloride, ferric chloride and the like. The concentration of initiator may be from 0.01 to 10 weight percent of the monomer being polymerized.

Coordination-type initiators usually involve a combination of a lower valent transition metal chloride with an organometallic compound. Specific combinations which are useful include diisobutylaluminum chloride with vanadium tris(acetylacetonate), diisobutylaluminum chloride with vanadium oxychloride) triisobutylaluminum with titanium tetrachloride, methlymagnesium bromide with titanium tetrachloride, lithium aluminumtetraecyl with titanium tetrachloride and the like. The concentration or' initiator may be from 0.01 to 10 weight percent of the monomer being polymerized.

Preferred reaction media for carrying out polymerizations initiated by coordination-type catalysts or the cationic catalysts are the hydrocarbons, particularly aliphatic hydrocarbons such as hexane and cyclohexane and the halogenated hydrocarbons such as tetrachloroethylene.

Reaction times can vary from a few seconds, i.e., 5 to several days, for example, two to three days or more depending on the particular monomer, initiator, solvent, and reaction temperature employed.

Pressures above and below atmospheric pressure are operable. Atmospheric and superatmospheric pressures are preferred.

The ho mopolymers of 1-acylbicyclo[1.1.0]butanes of this invention are high molecular weight, solid, thermoplastic polymers which are useful for preparing shaped objects of all sorts, such as films, fibers, tubes, pipes, bottles, and molded objects of many shapes. Solution casting, dry spinning from solution, melt extrusion, injection molding, compression molding, and blow molding may be employed.

The carbonyl function which is a fundamental characteristic of all the polymers of this invention may be subjected to further chemical reaction to vary the functionality of the polymer. Such reactions may be used for attaching a dye or color-forming group, particularly in fibers, and may serve as a functional group for crosslinking the polymer by reaction with a crosslinking agent, such as a polyalcohol, a polyamine, or the like.

The following examples illustrate the invention in further detail but are not meant to limit the invention in any respect. Unless otherwise indicated, parts are by weight.

EXAMPLE 1 Part A3-hydroxycyclobutanecarbonitrile To a stirred solution of 2.25 g. (0.060 mole) of sodium borohydride in 50 ml. of water was added with stirring a warm slurry of 19.0 g. (0.20 mole) of 3-cyanocyclobutanone in 50 ml. of water. The reaction was mildly exothermic and ice cooling was used to maintain the temperature at 35. After the addition was complete. the solution was stirred at room temperature for 4 hours and was extracted continuously overnight with chloroform. The chloroform extract was dried and distilled to give 16.79 g. (86.5%) of 3-hydroxycyclobutanecarbonitrile in the form of a colorless liquid, B.P. 71 (0.33 mm.).

Part B3-chlorocyclobutanecarbonitrile To a stirred solution of 14.03 g. (0.145 mole) of 3- hydroxycyclobutanecarbonitrile, 12.0 g. (0.152 mole) of dry pyridine and 25 ml. of chloroform was added at 0-5 a solution of 19.80 g. (0.166 mole) of thionyl chloride in 25 ml. of chloroform during 38 minutes. The solution was allowed to Warm to room temperature with stirring. With continued stirring during 2 hours, the temperature was raised to 56 and during an additional 2 hours to 65. The solution was cooled and washed with 500 ml. of water containing 10 ml. of 37% hydrochloric acid, with 500ml. of water containing 10 g. of sodium hydroxide, and with 500 ml. of water containing 10 g. of potassium chloride. It was dried with magnesium sulfate and distilled in a small spinning-band column to give 13.69 g. (81.7%) of 3-chlorocyclobutanecarbonitrile, B.P. 98 (28 mm.).

Part CPhenyl 3-chlorocyclobutyl ketone To a stirred solution of 13.8 parts 3-chlorocyclobutanecarbonitrile in parts of anhydrous ether in a system blanketed with nitrogen was added 21.8 parts phenylmagnesium bromide in 20 parts of ether. This mixture was heated under reflux for 3 hours and then poured into 200 parts of cold 6 N hydrochloric acid. The organic phase was separated and the aqueous phase extracted twice with 212.4 parts ether. The combined ether extracts were washed with 200 parts of saturated aqueous sodium bicarbonate. The product was isolated by vacuum distillation which gave 12 parts of phenyl 3-chlorocyclobutyl ketone, B.P. 76-78/7,LL-

AnaZysis.Calcd. for C H ClO: C, 67.90; H, 5.65; Cl, 18.25; M.W., 194.7. Found: C, 68.54; H, 5.68; Cl, 17.70; M.W., 191; C, 68.48; H, 5.64.

Part Dl-benzoylbicyclo 1.1.0] butane To a stirred solution of 4.5 parts of potassium tertbutoxide in 30 parts of dry tetrahydrofuran at -3 was added a solution of 6.6 parts of phenyl 3-chlorocyclobutyl ketone in parts of dry tetrahydrofuran. This mixture was then stirred at 0 for 1% hours. To this reaction mixture was added 75 parts of saturated aqueous potassium chloride. The organic layer was separated and washed twice with 25 parts each of saturated aqueous potassium chloride. The organic layer was dried over molecular sieves and the solvent evaporated under reduced pressure to yield l-benzoylbicyclo[1.1.01butane in the form of an oily liquid.

Part E-Poly l-benzoylbicyclo[1.1.0]butane The 1-benzoylbicyclo[1.1.0]butane obtained in Part D was allowed to stand overnight at room temperature. It polymerized spontaneously to a hard, brittle solid. The polymer was dissolved in 50 parts of benzene and precipitated in 500 parts methanol. The infrared spectrum showed a carbonyl band at 5.95;.t. The polymer showed an inherent viscosity of .04, at 25; Tg was observed at 138. The polymer was stable up to 421 C.

Analysis.Calcd. for [C H O] C, 83.52; H, 6.37. Found: C, 83.39; H, 6.58; C, 82.70; H, 6.50; C, 82.78; H, 6.54.

EXAMPLE 2 Part AMethyl 3-chlorocyclobutyl ketone To a stirred solution of 58 parts of 3-chlorocyclobutanecarbonitrile in 354 parts of anhydrous ether in a system blanketed With nitrogen was added 90.6 parts of methylmagnesium bromide in 82 parts of ether. This mixture was heated under reflux for one hour, and then poured into 250 parts of 3 N hydrochloric acid. The organic phase was separated and the aqueous phase extracted twice with 70 parts of ether each. The combined ether extracts were washed with 300 parts of saturated aqueous sodium bicarbonate and then with 300 parts of water. The products isolated by distillation under reduced pressure were 6 parts 1-cyanobicyclo[1.1.0]butane and 7 parts methyl 3-chlorocyclobutyl ketone, B.P. 80/ 10 mm. The infrared, NMR and mass spectra of the latter were consistent with the structure methyl 3-chlorocyclobutyl ketone.

Part B--1-acetylbicyclo[ 1.1.0] butane To a stirred mixture of 1.20 parts of sodium hydride in 50 parts of distilled N-methylpyrrolidone under a blanket of nitrogen was added 6.6 parts methyl 3-chlorocyclobutyl ketone. The mixture was stirred at -25" until hydrogen evolution ceased. The mixture was then poured into 200 parts ether and 100 parts of saturated ammonium chloride. This mixture was shaken in a separatory funnel and the organic layer separated. The ether layer was washed twice with 100 parts of cold water. The ether extract was then dried over molecular sieves and the ether evaporated under reduced pressure. The remaining product was distilled to give 0.56 part of 1- acetylbicyclo[l.1.0]butane, B.P. 39/ 8 mm. The infrared and NMR spectra were in accordance with the proposed structure.

6 Part C-Poly l-acetylbicyclo[1.1.0]butane When a sample of 1-acetylbicyclo[1.1.01butane was dissolved in carbon tetrachloride and allowed to stand overnight at room temperature, a white polymer formed. A transparent, tough film was cast from a dimethylformamide solution. The polymer showed an inherent viscosity at 1.96 at 25 in dimethylformamide.

EXAMPLE 3 Part A3chlorocyclobutanecarboxaldehyde To a solution of 15.5 parts of phenyl 3-chlorocyclobu tanecarboxylate in 5 parts of tetrahydrofuran at 0 C. was added 13.9 parts of lithium tri-tert-butoxy-aluminohydride in 57 parts of tetrahydrofuran. This mixture was stirred at 0 for 4 hours and hydrolyzed with 10 parts 5 N sulfuric acid. The organic layer was separated and the aqueous layer extracted twice with parts of pentane. The combined extracts were washed with 100 parts 5% sodium bicarbonate and four 100 parts of water. Distillation gave 5.5 parts of 3-chlorocyclobutanecarboxaldehyde, B.P. 70-74/21 mm. The 2,4-dinitrophenylhydrazone derivative showed a melting point of 168169.

AYZQIYSLS'w-CfilCd. for C11H11C1N404: C, H, 3.71; Cl, 11.90; N, 18.70. Found: C, 44.37; H, 3.62; Cl, 12.93; N, 18.48.

Part B-1-bicyclo[1.1.0]butanecarboxaldehyde To a stirred mixture of 0.72 part of sodium hydride in 75 parts of dry N-methylpyrrolidone under a blanket of nitrogen was added 3.7 parts of 3-chlorocyclobutanecarboxaldehyde. This mixture was stirred until hydrogen evolution ceased and was then treated with a mixture of 100 parts of ether and parts of a saturated aqueous ammonium chloride solution. The organic layer was separated and the aqueous layer was extracted twice with 100 parts of ether. The combined ether extracts were Washed once with 500 parts dilute hydrochloric acid (pH 3) and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the product distilled to give 0.8 part of 1-bicyclo[1.1.0]bu tanecarboxaldehyde, B.P. 4146/30 mm. The infrared and NMR spectra were in accordance with the proposed structure. The mass spectrum showed the product to be present.

Part C-Poly l-bicyc1o[ 1.1 .0] butanecarboxaldehyde The aldehyde obtained in Part B polymerized to a clear tough polymer when it was allowed to stand overnight at room temperature.

EXAMPLE 4 Part APheny1 3-methylenecyclobutyl ketone To a solution of 9.3 parts of 3-methylenecyclobutanecarbonitrile in 100 ml. of ether was added 18.1 parts phenylmagnesium bromide in 150 parts ether. This mixture was heated under reflux for 2 hours. This mixture was then poured into 200 parts cold water and 36 parts HCl and stirred for 30 minutes. The organic layer was separated and dried over anhydrous sodium sulfate. Evaporation of the solvent gave 15 parts of phenyl 3-methylenecyclobutyl ketone. A 2,4-dinitrophenylhydrazone derivative showed a melting point of 119-121 Analysis.-Calcd for C18H14N404: C, H, N, 15.90; M.W., 352. Found: C, 61.63; H, 4.50; N, 15.81; M.W., 341; C, 61.63; H, 4.59; N, 16.00.

Part B3-methyll-benzoylbicyclo 1. 1 .0] butane To 255 parts of 55-58% hydroiodic acid cooled with an ice bath was added with vigorous stirring 25.6 parts of phenyl 3-methylenecyclobutyl ketone. This mixture was stirred at 0 for one hour and at 25 for 2 hours. The layers were separated, and the aqueous layer was extracted with methylene chloride. The combined organic and methylene chloride layers were rinsed with 100 parts of water, decolorized with 100 parts 5% sodium thiosul- 7 8 fate, dried over anhydrous sodium sulfate, filtered, and were separated, and the aqueous layer was extracted with the solvent removed in vacuo. There was obtained 54.2 methylene chloride. The combined organic and methylene parts of cisand trans-phenyl 3-iodo-3-methylcyclobutyl chloride layers were rinsed with 100 parts of water, de-

ketone. This was added to 126 parts of anhydrous ether colorized with 100 parts 5% sodium thiosulfate, dried and 4.1 parts sodium hydride and stirred at room temover anhydrous sodium sulfate, filtered, and the solvent perature for 36 hours. This mixture was filtered and the removed in vacuo. There was obtained 35.4 parts of methsolids washed with 8 to 10 parts of ether. The combined yl 3-iodo-3-methylcyclobutyl ketone. This was added to ether extracts were washed with water and then dried 100 parts of anhydrous ether and 4.0 parts sodium hyover anhydrous sodium sulfate. The solvent was evapodride and stirred at room temperature for 36 hours. This rated and the product distilled under reduced pressure 10 mixture was filtered and the solids washed with 8 to l0 to give 12 parts of 3-methyl-l-benzoylbicyclo[1.1.01buparts of ether. The combined ether extracts were washed tane, B.P. 6770/ 15 mm. The infrared and NMR specwith water and then dried over anhydrous sodium sulfate. tra were consistent with the assigned structure. The solvent was evaporated and the product distilled under reduced pressure to "ive 3.4 parts of 1-acetyl-3- EXAMPLE 5 15 methylbicyclo[l.l.0]butane, 3P. 6365/10' mm. The in- Paft y 3'methY1eneCYC10but3/1 kfitone frared ad NMR spectra were consistent with the assigned To 88.9 parts of 3-methylenecyclobutanecarbonitrile Structurep in 1000 parts of dry ether was added 125 parts methyl- When the Gngnard {eagents shown In column A M magnesium bromide in 225 parts of ether. This mixture Tabb 1 below are Subsmuted for methylmagneslum was heated under reflux for one hour and then poured mide in the Pmcedure of Part of Example the i into 40 parts HCl in 200 parts cold water. The organic Gated l-acyl-3-halocyclobutanes 1n column B are' obtained. layer was separated and the aqueous layer was extracted When these are substituted for methyl 3-ch'lorocyclobutyl twice with 400 parts each of ether. The combined ether ketone 111 the Procedure of Part B of EXample the extracts were washed with 500 parts of saturated aqueous l-acylbicyclotl-l-olbutanes of column C are Obtainedsodium bi b and then dried Over anhydrous The bicyclo[l.1.0]butanes of column C are converted to dium sulfate. The solvent was evaporated to give 85 parts high 1110160111? ll/Fight Polymers y heating the PE of methyl 3-methylenecyclobutyl ketone, B.P. 7072/ 40 ence a free radlcal-type catalyst, Such as 3101313150- butyronitrile.

Analysis calcd f C7H1OO; c 7 33; H, 9 1 5 When the 1-cyano-3-alkylenecyclobutanes shown in Found; 7531; H, 93 C, 7521; H, 9 37 column A of Table II below are substituted for 1-cyano-5- methylenecyclobutane in the procedures of Example 4. Part Ji3' 1-acetyl'3'methylblcyclo[1'l'mbutane Parts A and B, the l-acyl-3-alkyl-3-iodocyclobutanes of To 255 parts of 55-58% hydroiodic acid cooled with column B and the l-acyl-3-alkylbicyclo[1.1.0]butanes of an ice bath was added with vigorous stirring 28.8 parts of column C are obtained. By further substitution of the methyl 3-methylenecyclobutyl ketone. This mixture was Grignard reagents of column A in Table I for the phenylstirred at 0 for 1 hour and at 25 for 2 hours. The layers magnesium bromide of the procedure of Example 4 as TABLE I Item (A) Grignard Reagent (B) 1-acy1-3-halocyclobutane (O) 1-acylbicyclo[1.1.0]butane 1 Allylmagnesium chloride 1-(S-butenoyl)-3-chlorocyclobutane 1-(3-butenoyl)bicyclo[1.1.0]butane. 2 Benzylmagnesium bromide. l-(pheuylaeetyl)-3-chlorocyelobutane l-(phenylacetyl)bicyclo[1.1.0]butane. 3 Z-butenylmagnesium bromide 1-(3-pentenoyl)-3-ehlorocyclobutane... 1-(3-pentenoyl)bicycl0[1.1.0]butane. 4 Cyclopropylmethylmagnesium bromide. 1(cyclopropylacetyl)-3-ehloroeyclobutane.. l-(cyclopropylacetyl)bieyelo[1.1.0]butane. 5 1,l-diethylpropylmagnesium bromide l-(triethylacetyl)-3-ehlorocyclobutane l-(trimethylaeetyl)bicyclo[1.1.0]butane. 6 3,7-%imethyl-2,6-octadienylmagnesium chlo- 1-S3 ,S-dimethyl-3,7-nonadienoyl)-3-chlorocyclo- 1-(a,8dimethyI-3,7-nonadenoyl)bieyelo[1.l.0]-

r1 e. u ne. u ane. 7 Q-anthrylmagnesium bromide 1-(Q-anthrylformyl)-3-chlorocyclobutane l-( -anthrylfonnyl)bicyc1o[1.1.0]butane.

- l-(cyclopropylformyl)bicyclo[l.1.0]butane. l-(cyclohexylformyllbieyelofl.1.0]butene. l-(Zheptynoyl)bicyclo[1.1.0]butane.

l-(l-naphthylformyl)bieycl0[1.1.0]butane. l-nonadeeoylbieybloUJ.0] butane.

l-(cyclopropylformyl)-3-chlorocycl0butane-. l-(cyelohexylformyl)-3-chloroeyclobutane- I-(Z-heptynoyl)-3-ehlorocyelobutane l-(l-naphthylformyl)-3chlorobutane. 1-nonadecoyl- -chlorocyclobutane Cyclopropylmagnesium chloride. Cyclohexylmagnesium bromide. l-hexynylmagnesium bromide.-- l-naphthylmagnesium bromide Octadeeylmagnesium chloride...

. l-octadecenylmagnesium chl0ride-- 1-(Z-nonadecenoyl)-3-ehlorocyclobutane 1-(2nouadecenoyl)bicyclo[1.1.0]butane.

2,5-xylylmagnesium chloride... 1-(2,5-dimethy1beuzoyl)-3-ehlorocyclobutane..- 1-(2,5-dimethylbenzoyl)bicyclo[l.1.0] butane. Durylmagnesium bromide 1-(2,3,5,6-tetramethylbenzoyl)-3-chlorobutane.. 1-i2,3,5,6-tetramethylbenzoyl)bieyc10[l.0.0]buane. 2,2-diphenylpropylmagnesium chloride 1-(3,3diphenylbutyryl)-3-ehloroeyclobutane.-- 1-(3,3-diphenylbutyryl)bicyclo[l.1.0]butane. -biphenylylmagnesium chloride. 1-(4-phenylbenzoyl)-3-chlorocyclobutane... 1-(4-phenylbeuzoyl) bicyclo[1.l.0] butane. Cinnamylmagnesium bromide. 1(4-phenyl-3-buten0yl)si-chlorobutane 1-(4-phenyl-3-butenoyl)bicyclo[1.1.0]butane. 1-cyclohexen-l-ylmagnesium chloride 1-(l-cyelohexen-l-ylformyl)-3-eh1orocyclobu- 1-gl-cyclohexen-l-ylformyl)bicyclo[l.1.0]butane. ane. Cyelopentadienylmagnesium bromide 1-(cyelopentadienylformyl) 3-chlorocyelobu- 1-(cyclopentadienylformyDbicycloIl.1.0]butame. tane. Ethylnylmagnesium bromide l-propioloyl-3-chlorocyc1obutane 1-propioloylbicyclo[1.l.0]butane. Z-naphthylmethylmagnesium chlorid 1-(2-naphthylaeetyl)-3-ehlorocyclobutane. l-(2-naphthylaeetyl)bieyclo[1.1.0]butane.

1-(Z-hexadeeylacryloyl)-3 chlorocyclobuta l-(Zhexadecylaeryloyl)bicyelo[1.1.0]butane. 1-acryloyl-3-ehlorocyelobutane-. 1-acryloylbieyelo[1.l.0]butane. 1-cinnamoyl-3-chlorocyclobutan l-cinnamoylbicycloIl.1.0] butane.

l-hexadecylvinylmagnesium chloride. Vinylmagnesium bromide. Styrylmagnesiurn bromid Terphenylylmagnesium chl o-Fluorophenylmagnesium bromide l-(o-fiuorobenzoyl)3-chlorocyclobutane 1(0-fluorobenzoyl)bicyclo[1.1.0]butane. p-Bromophenylmagnesiurn bromide. l-(p-bromobenzoyl)-3-chlorocyclobutane 1-(p-bron1obenzoyl)bicyclo[1.1.0]butane. Pentachlorophenylmagnesium ehlorid l-pentaehlorobenzoyl-3-chlorocyclobutaue. l-pentachlorobenzoylbicyclo[1.1.0]butane. 3-ehloro-4-ethoxyphenylmagnesium ch10 l-(3-cgiloro4-ethoxybenzoyl)-3-chloroeyelo- 1-gi-thloroiethoxybenzoyl)bicyclo[1.l.0]-

bu ane. u aue. 31--... 3-ch1oro-1-naphthylmagnesium chloride 1gs-chlor0-1-na.phthy1formyl)-3-chlorocyclo- 1-(3-chloro-1-naphthylformyl)bieyelo[1.1.0}-

utane. butane. 32.-... p-(2iethoxymethyl)phenylmagnesium chlo- 1-{lp-[diethoxymethyl]benzoyl)-3-chlorocyclol-(lp-[diethoxymethyflbenzoyl)bicyclo[1.1.0]-

1i e. utane. utane. 33..-.- 2,2-difluoroethylmagnesium chloride 1-(3,3-diiluoropropionyl)-3-ohlorocyclobutane. 1-(3,3-ditluoropropionyl)bicycl0[1.1.0]butane. 34.-." S-ethoxy-Z-methylpropenylmagnesium bro- 1-(4ethoxy-3-methyl-2-butan0yl)-3-chlorocy- 1-( i-ethoxy-3-methyl-2-butenoyl)bicyclo[1.1.0]

mide. elobutane. butane. 35..- Heptafluoropropylmagnesium bromide l-heptafluorobutyryl-3-chloroeyclobutanel-heptafluorobutyrylbicycloIl.1.0]butane. 36. 4-meth0xy-2-naphthylmagnesium bromide.. 1-(g-methoxy-Zmaphthylformyl) 3-chl0rocycl0- l-gi nethoxyQ-naphthylformyl)bicyclo[1.l.0]-

utane. utane. 37..-.. Trifluoromethylmagnesium iodide 1-trifluoroaeetyl-Zi-chlorocyclobutane l-trifluoroacetylbicyclo[1.l.0]butui1e.

38... Trifiuorovinylmagnesium iodide l tritluoroacryloyl-3-chlorocyclobutane l-trifluoroacryloylbicyclo[1.l.0]butane.

6. The compound of claim 1 having the name 3- methyl- 1 -benzoylbicyclo 1 l .0] butane.

7. The compound of claim 1 having the name l-acetyl- 3 -methylbicyclo[ 1. 1 .0] butane.

8. A film and fiber forming homopolymer of the a coordination-type initiator as shown above.

monomer defined in claim 1.

TABLE II Item (A) 1-cyano-3-alkylenecyclobutane (B) 1-acyl-3-alkyl-3-i0doeyclobutane (C) 1-aeyl 3-alkylbicyclo[1.1.0]butane 1 l-cyan-3-Inethylene-Z-phenyleyclobutane l-benz0yl-3-iodo-3methy1-2-phenyleyclobu- Hie/n2oyl-3-methyl-2-phenylbicyclo[1.1.0]butune. ans. 2 l-cyano-2,2-diethyl-3-methylenecyelobutane- 14%enzoyl-2,2-diethyl-3-iodo-3-rnethylcyclol-ligenz0yl-2,2-diethyl-3-methylbicyclo[1.1.0]-

utane. utaue. 3 1-cyar1o-3 isopropylidenecyclobutane l-benzoyl-3-iodo-3-isopropyleyclobutane l-benzoyl-3-isopropylbicyclo[1.1.0]butane. 4 l-cyano-2,2-di(n-butyl)-4-metl1yl-3-n1ethylene- 1benz0yl-2,2-di(n-butyl)-3-10do-3,4-dm1ethyl- 1-benzoyl-2,2-di(n-butyl)-3,4-dimethylbieyclocyclobutane. cyclobutane. [1.1.0]butane. 5 1-cyan0-2-rnethyl-3'(5-nonylidene)cycl0butane l-tgenzoyl-3-iodo-2-methyl-3-(5-n0nyl)cyclo- 1-l%eIzoyl-2-methyl3-(5-nonyl)bicyclo[l.1.0]-

utane. u ane. 6 l-cyano-Z-dodecyl3 methylene-4-phenylcyclo- 1benz0yl-2-dodecyl-3-iodo-3-methyl-4pheuyl- 1-benz0yl-2-dodecyl-3-methyl-4-phenylbicyelobutane. butane. [1.1.0]butane. 7 1-cyan0-2-phenyl-3-tridecylidenecyclobutane l-benzoyl-3-iodo-Z-phenyl-B-tndecyclobutane l-bfinioyl-Z-phenyl-3-tridecylbicyclo[1.1.0]

u ane. 8 2-n-butyl-1cyano-3-(Q-heptadecylidene)-2- l-benzoy1-2-n-butyl-3-(El-heptadecyl -3-i0do-2- l-benzoyl-2-n-butyl-349-heptadecyl)-2-methylmethylcyclobutane. methylcyclobutane. bicyclo[1.1.0]butane. 9 1cyano4decyl-3-isopropylidene2,2-di methyl- 1-benzoyl-4-decyl-3-iodo-3-1sopr0py1-2,2-d1 l-benzoyl--decyl3-isopropyl-2,2-dimethylbicyclobutane. methylcyclobutane. cyclo[1.1.0]butane. 10 l-cyauo-4-cyclohexyl-2-cyclopropy1-2-methyll-benz0yH-cyclohexyl-Z-cyclopropyl-IZ-iodol-benz0yl--cyclohexyl-Z-eyclopropyl-Z,3-di- 3-methylenecyclobutane. 2,3-dimethylcyclobutane. methylbicycloUJ .0]butane. 11 1-cyan0-3-cycl0hexylmethylene-Z-cyclopropyll-benzoyl-3-cyclohexylmethylQ-cyclopropyll-benzoyl 3-cycl0hexylmethyl-lcyclopropyl- 2methylcycl0butane. 3-iodo-2-methylcyclobutane. 2-methylbicyelo[1.1.0]butane. 12"... 2benzyl-1cyan0-2rnethyl-3-methylene+tril-benzoyl-Q-benzyl 3-10do-2,3-dimethyl-4-tril-benzoyl-Z-benzyl-2,3-dimethyl-4-tridecylbidecylcyclobutane. decylcyclobutane. cyclo[1.1.0]butane. l3--. 2-benzyl-l-cyano-2-methyl-3-tetradecylidenel-benz0yl-2-benzyl-3-1odo-2-methyl-3-tetradel-benzoyl-Z-benzy1-2-methyl-3tetradeeylbicyclobutane. cylcyclobutane. cyclo[1.1.0]butane. l4 l-cyano-Ii-methylene-2,Z-diphenylcyclobutane 1b;ntz0y1-3-iodo-3-methyl-2,2-diphenylcyclol-bgantzoyl-3-methyl-2,2-dipl1eny1bicyclo[l.l.0]-

u ans. u ane. 15 1-cyano-3-methylene-2-(fi-naphthyl)cyclobul benzoyl-3 iodo-3-methyl-2-(B-napl1thyl)cy- 1-benz0yl-3-methyl-2-(B-naphthyDbicyclotane. obutane. [1.1.0]butane. 16 1-cyan0-2-(ornaphthyl)-2-phenyl-3-(1-phenyll-benz0yl-3-iodo-2(a-naphthyl)-2-phenyl-3-(1- 1-benzoyl-2-(a(-naphthyl)-2-pheny1-3-(1-phen- 1 p-tolyl)-methylenecyclobutane. phenyl-1p-tolyl)methylcyclobutane. yl-l-p-tolyl)methylbicyclofl.1.0]butane. 17..." 1-cyano-3-(fi-cyclohexylethylidene)cyclobul-bgentzoyl-3 (B-cyclohexylethyl)-3-1od0cyclol-bgntzoyl-3-(fl-cyelohexylethyl)bicycloh.1.0]-

tane. u ane. u ane. 18 1-cyano-2-cyclohexylmethyl-K-methyleneeyl-benzoyl-2-cyclohexylmethyl-3-iodo-3-methl-benzoyl-2-cyclohexylmethyl-3-methylbicyclobutaue. ylcyclobutane.

The foregoing detailed description has been given for clearne'ss of understanding only and no unnecessary limitations are to be understood therefrom. The invention is cyc1o[1.1.0]butane.

9. Process for preparing compounds of claim 1 which comprises reacting a compound of the formula not limited to the exact details shown and described, for 40 obvious modifications will occur to those skilled in the art. 4 5 0 The embodiments of the invention in which an eX- R H elusive property or privilege is claimed are defined as R follows: X 1. A compound of the formula R1 R4 R5 R4 R5 V i V i R -0R and C-R A X H wherein R, R R R R and R are defined as in claim 2 1 wherein R2 1 1 and X is a halogen of atomic number 17 through 53,

R is selected from the class consisting of hydrogen, hydrocarbyl of 1 to 19 carbon atoms, and substituted bydrocarbyl of 1 to 19 carbon atoms in which the substituents are selected from the class consisting of halogen, lower alkoxy and mixtures thereof and R R R R and R are each individually selected from the class consisting of hydrogen and hydrocarbyl of 1 to 19 carbon atoms that is free of aliphatic unsaturation.

2. A compound of claim 1 wherein R is hydrogen, lower alkyl or phenyl and R R R R and R are each hydrogen or lower alkyl.

3. The compound of claim 1 having the name l-benzoyl-bicyclo[ 1.1.0] butane.

4. The compound of claim 1 having the name l-acetylbicyclo[ 1. 1 .0] butane.

5. The compound of claim 1 having the name 1- bicyclo-[1.1.01butanecarboxaldehyde.

with a dehydrohalogenating agent.

10. Process which comprises polymerizing a compound of claim 1 in the presence of an organic solvent and an initiating catalyst, and at a temperature of between WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner US. Cl. X.R.

3 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 85,798 Dated December 23, 1969 Inventor s) 0181130111118 D Smith It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, 1. 20, insert and between "above" II n,

and n Col. 3, 1. 4, insert a comma between "helium" and "argon"; line 75, correct spelling of aluminumtetradecyl Col. 8, l. 16, correct spelling of and Table I, Item 5, col. "(0)", change "l-(trimethylacetyl to 1-(triethylacetyl)--; Item 11, col. "(B)", change "chlorobutane" to chlorocyclobutane Item 15, col."(B)" change "chlorobutane" to chlorocyclobutane Item 15 co1."(C) change "bicyclo[l.0.0]" to bicyclo[1.l.0] --5 Item 18, col. "(B)", change "chlorobutane" to chlorocyclobutane Item 34, col. "(B)", change "butanoyl" to butenoyl and Item 36, change "l-(o-. to l-(6-.. in col. "(B)";

Table II, Item 6, col. "(B)", change .phenylbutane" to .phenylcyclobutane Item 7, col. "(B)", change .-tridecyclobutane. to .-tridecy1cyclobutane. and

Claim I, delete the formula within the brackets.

SIGNED AND SEALED AUG 4 .1970

Anew Ed (I M. Fl tch WILLIAM E. sum, JR- Attestmg Offlcer flommissione-r of Patents 

